CN1231500C - Catalyst for polymerization and copolymerization of ethylene - Google Patents

Catalyst for polymerization and copolymerization of ethylene Download PDF

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Publication number
CN1231500C
CN1231500C CNB028028929A CN02802892A CN1231500C CN 1231500 C CN1231500 C CN 1231500C CN B028028929 A CNB028028929 A CN B028028929A CN 02802892 A CN02802892 A CN 02802892A CN 1231500 C CN1231500 C CN 1231500C
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compound
magnesium
catalyzer
titanium
hydroxyl
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CN1527843A (en
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杨春炳
金湘烈
李源
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Hanwha Total Petrochemicals Co Ltd
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Samsung General Chemicals Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/646—Catalysts comprising at least two different metals, in metallic form or as compounds thereof, in addition to the component covered by group C08F4/64
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

A solid titanium complex catalyst for polymerization and copolymerization of ethylene is prepared by the process comprising: (1) preparing a magnesium solution by reacting a halogenated magnesium compound with an alcohol; (2) reacting the magnesium solution with an ester compound having at least one hydroxyl group and a silicon compound having at least one alkoxy group to produce a magnesium composition; and (3) producing a solid titanium catalyst through recrystallization by reacting the magnesium composition solution with a mixture of a titanium compound and a haloalkane compound; and optionally reacting the solid titanium catalyst with an additional titanium compound. The solid titanium complex catalyst for polymerization and copolymerization of ethylene according to present invention exhibits high catalytic activity, high hydrogen reactivity and controlled particle size, and can be advantageously used in the polymerization and copolymerization of ethylene to produce polymers of high bulk density.

Description

The polymerization of ethene and copolymerization catalyzer
Technical field
The present invention relates to the polymerization and the copolymerization catalyzer of ethene.More particularly, the present invention relates to the polymerization and the copolymerization solid titanium composition catalyst of ethene.The embodiment of catalyst system comprises the solid titanium composition catalyst that is carried on the magnesium-containing carrier.This catalyzer demonstrates the hydrogen reaction good in high catalytic activity, the polymerization process and the granularity of control, thereby can produce the polymkeric substance of high-bulk-density.
Background technology
Usually in the presence of solvent such as iso-pentane or hexane, in liquid phase or in gas phase, carry out the polymerization of ethene.In these technologies, influence polymerization activity that the polymeric important factor is a catalyzer and hydrogen reaction, resulting polymers tap density, dissolve in amount of monomer in the solution, size distribution and the existence of particulate in resulting polymers.Hydrogen reaction can be normally defined in the polymerization and polymerization process of ethene, and the molecular weight of the polymkeric substance of being produced is with the intensity of variation of employed amounts of hydrogen, so that the molecular weight of controlling polymers.Have the catalyzer of high hydrogen reaction by use, under the situation that adopts small amounts of hydrogen, the molecular weight of controlling polymers effectively, thus in the operation of polymerization technique, provide handiness.
Recently, reported many methods, it uses magniferous titanium-catalyst based as olefinic polymerization and copolymerization catalyzer.These catalyzer high catalytic activity can be provided and produce high-bulk-density polymkeric substance and known they be suitable for the liquid and gas polymerization.
For example, using magnesium solution, when obtaining catalyzer (this catalyzer can produce the olefin polymer of high-bulk-density), by making the reaction of magnesium compound and electron donor(ED), the preparation magnesium solution.Electron donor(ED) comprises alcohol, amine, cyclic ethers or organic carboxyl acid.In the presence of varsol, prepare magnesium solution.Can be by making magnesium solution and halogen contained compound such as titanium tetrachloride reaction, the catalyzer of preparation magnesium carrying.In US Patent No s3642746,4336360,4330649 and 5106807, disclose and used alcohol to prepare the method for magnesium solution.In addition, United States Patent(USP) Nos. 4477639 and 4518706 discloses and has used tetrahydrofuran (THF) or cyclic ethers as the method for dissolved magnesium compound with solvent.Although these catalyzer can produce the polymkeric substance of high-bulk-density, need improve catalyzer aspect catalytic activity and the hydrogen reaction.
In addition, United States Patent(USP) Nos. 4847227,4816433,4829037,4970186 and 5130284 had been reported the preparation of olefin polymerization catalysis, and this catalyzer has good polymerization activity and can improve the tap density of resulting polymers.By make electron donor for example the reaction of alkoxyl magnesium, bialkyl ortho phthalate (salt) or phthalyl chloride and titanium chloride compound can realize the raising of polymerization activity.United States Patent (USP) 5459116 has been put down in writing a kind of method for preparing the titanium solid catalyst, that is: make to contain at least one hydroxyl and contact with titanium compound as the magnesium solution of electron donor.Adopt this method, can obtain having the catalyzer of high polymerization activity and high-bulk-density is provided in resulting polymers; However, for hydrogen activity, still need to improve greatly.
At last, U.S. Patent No. 5869418 discloses in the polymerization process of propylene, by using external electronic donor, improves the method for the hydrogen reaction of catalyzer, and has set forth its advantage.Yet except solid catalyst, the application limitations of this method of also using external electronic donor is in the polymerization and the copolymerization of propylene.
Therefore, need be used for the catalyzer of vinyl polymerization and copolymerization, this catalyzer can prepare by simple technology, has high polymerization activity and hydrogen reaction.In addition, there is demand in the catalyzer that can produce the narrow size distribution and the polymkeric substance of a small amount of particulate.
Disclosure of the Invention
The objective of the invention is the polymerization and the copolymerization catalyzer that solve above-mentioned the problems of the prior art and ethene is provided.More particularly, the purpose of this invention is to provide a kind of catalyzer, it has the catalyst grain size of desired high catalytic activity, control in the polymerization of ethene and copolymerization, so that provide resulting polymers high tap density, with high hydrogen reaction, thus controlled polymerization technology easily.
Detailed description of preferred embodiments
In one embodiment, can be by the polymerization and the copolymerization catalyzer of the prepared ethene that comprises the steps, this catalyzer has high catalytic activity and hydrogen reaction, and can produce the polymkeric substance of high-bulk-density:
(1) by being contacted with alcohol, halogenated magnesium compound prepares magnesium solution;
(2) this magnesium solution is reacted with the ester cpds with at least one hydroxyl with the silicon compound with at least one alkoxyl group and produce the solution that contains magnesium component; With
(3) by making the solution that contains magnesium component and the mixture reaction of titanium compound and compound halo alkane produce solid titanium catalyst.
The polymerization of preparation ethene and copolymerization randomly comprise further step with the method for catalyzer:
(4) make solid titanium catalyst and extra titanium compound reaction.
The polymerization of preparation ethene and the method that catalyzer is used in copolymerization below will be described in more detail.
By making halogenated magnesium compound and pure contact preparation magnesium solution.
In one embodiment, magnesium compound can be a halogenated magnesium compound.The type of halogenated magnesium compound used in the present invention can comprise following magnesium dihalide compound such as magnesium chloride, magnesium iodide and magnesium fluoride; Alkyl halide magnesium compound such as methylmagnesium-halide, ethyl magnesium halide, propyl group magnesium halide, butyl magnesium halide, isobutyl-magnesium halide, hexyl magnesium halide and amyl group magnesium halide; Alkoxyl group halogenated magnesium compound such as methoxyl group magnesium halide, oxyethyl group magnesium halide, isopropoxy magnesium halide, butoxy magnesium halide and octyloxy magnesium halide; Aryloxy magnesium halide such as phenoxy group magnesium halide and methylphenoxy magnesium halide.Can use magnesium compound with single compound form or with the form of mixtures of two or more compounds.In addition, can use above-mentioned magnesium compound with title complex compound form effectively with other metal.
The compound that can not represent with molecular formula that other magnesium compound comprises that the production method that depends on magnesium compound may occur, this compound can be commonly referred to be the mixture of magnesium compound.For example, following compound can be used as magnesium compound: this compound that obtains by the silane compound reaction that makes magnesium compound and polysiloxane compound, halogen-containing, ester or alcohol; With in the presence of halogenated silanes, phosphorus pentachloride or thionyl chloride, by this compound that MAGNESIUM METAL and alcohol, phenol or ether reaction are obtained.
In some embodiments, magnesium compound can be magnesium halide, particularly magnesium chloride or the alkylmagnesium chloride with alkyl of 1-10 carbon atom, have 1-10 carbon atom alkoxyl group alkoxy-magnesium chloride and have the aryloxymagnesium chloride of the aryloxy of 6-20 carbon atom.
Existing or not existing under the varsol, be dissolved in the alcohol by making magnesium compound, can prepare employed magnesium solution.
The type of varsol used in the present invention can be aliphatic hydrocrbon such as pentane, hexane, heptane, octane, decane and kerosene; Clicyclic hydrocarbon such as phenyl ring, methyl ring benzene, hexanaphthene and methylcyclohexane; Aromatic hydrocarbon such as benzene,toluene,xylene, ethylbenzene, cumene and cymene; With halon such as propylene dichloride, ethylene dichloride, trichloroethane, tetracol phenixin and chlorobenzene.
Exist or do not exist under the varsol (as previously discussed), using alcohol, can prepare magnesium solution by magnesium compound as solvent.The type of alcohol can comprise the alcohol that contains 1-20 carbon atom, alcohol as methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, hexanol, octanol, decyl alcohol, dodecanol, Stearyl alcohol, phenylcarbinol, phenylethyl alcohol, Isobutyl Benzyl Carbinol and cumyl alcohol and the optional self-contained 1-12 carbon atom of preferred alcohol.
The mean sizes of gained catalyzer and size distribution can be depending on the ratio of the type of the type of employed alcohol and consumption, magnesium compound and magnesium compound and alcohol.The consumption that obtains the employed alcohol of magnesium solution is 0.5mol at least, maybe can be about 1.0-20mol, or 2.0-10mol/mol magnesium compound more preferably from about.
In the preparation process of magnesium solution, can in the presence of hydrocarbon, carry out magnesium compound and pure reaction.Although temperature of reaction can change with the variation of the type of employed alcohol and consumption and can be at least about-25 ℃, preferred-10-200 ℃, or more preferably from about 0-150 ℃, the reaction times can be about 15 minutes-5 hours, or preferred about 30 minutes-4 hours.
The magnesium solution of step (1) preparation can with as the ester cpds with at least one hydroxyl of electron donor(ED) with have the silicon compound reaction of at least one alkoxyl group, form magniferous composition.
In the middle of electron donor(ED), ester cpds with at least one hydroxyl comprises the unsaturated aliphatic acid esters with at least one hydroxyl, as vinylformic acid 2-hydroxyl ethyl ester, methacrylic acid 2-hydroxyl ethyl ester, vinylformic acid 2-hydroxypropyl acrylate, methacrylic acid 2-hydroxypropyl acrylate, vinylformic acid 4-hydroxy butyl ester, pentaerythritol triacrylate; The aliphatic mono or polyester such as the acetate 2-hydroxyl ethyl ester that have at least one hydroxyl separately, the 3-beta-hydroxymethyl butyrate, ethyl 3-hydroxybutanoate, the 2-hydroxy-methyl isobutyl acid, the 2-ethyl butyrate of hydroxyl iso, propionic acid methyl-3-hydroxyl-2-methyl esters, 2,2-dimethyl-3-hydroxy propionate, the 6 hydroxycaproic acid ethyl ester, the tertiary butyl-2-hydroxy-iso-butyric acid ester, 3-hydroxyl ethyl glutarate, ethyl lactate, isopropyl lactate, lactic acid butyl isobutyl ester, isobutyl lactate, ethyl mandelate, tartrate dimethyl ethyl ester, ethyl tartrate, dibutyl tartrate, the lemon diethyl ester, triethyl citrate, 2-hydroxy ethyl caproate and two (methylol) diethyl malonate; Aromatic ester such as phenylformic acid 2-hydroxyl ethyl ester, Whitfield's ointment 2-hydroxyl ethyl ester, benzoic acid methyl-4-(hydroxy methyl), 4-methyl hydroxybenzoate, 3-nipagin A, 4-cresotinic acid acid esters, salicylic ether, salol, 4-nipasol, 3-hydroxyl naphthalic acid phenyl ester, monoethylene glycol mono benzoate, diglycol monotertiary benzoic ether and triglycol mono benzoate with at least one hydroxyl; With alicyclic ester with at least one hydroxyl such as hydroxybutyrolactone.
Consumption with ester cpds of at least one hydroxyl is a 0.001-5mol/mol magnesium, or preferred 0.01-2mol/mol magnesium.
As the silicon compound with at least one alkoxyl group, it is used as another kind of electron donor(ED) in step (2), can use general formula R in some embodiments 1 aR 2 bR 3 cR 4 dSi (OR 5) eThe compound of expression, wherein R 1, R 2, R 3, R 4, and R 5Respectively doing for oneself has the hydrocarbon of 1-12 carbon atom, and they can be same to each other or different to each other separately, and a, b, and c, d and e are 0 to 4 integers, and satisfy formula a+b+c+d+e=4.
For example, can use following compound: dimethyldimethoxysil,ne, dimethyldiethoxysilane, dimethoxydiphenylsilane, the aminomethyl phenyl methoxy silane, the phenylbenzene diethoxy silane, ethyl trimethoxy silane, vinyltrimethoxy silane, methyltrimethoxy silane, phenyltrimethoxysila,e, Union carbide A-162, ethyl triethoxysilane, vinyltriethoxysilane, the butyl triethoxyl silane, phenyl triethoxysilane, ethyl three isopropoxy silane, vinyl three butoxy silanes, tetraethyl silicate, butyl silicate or methyl three aryloxy silanes.
The consumption of these compounds can be about 0.05-3mol, or preferred 0.1-2mol/mol magnesium.
The suitable temp of the reaction of magnesium solution, the ester cpds with at least one hydroxyl and alkoxy-silicon compound is 0-100 ℃, or more preferably 10-70 ℃.
With general formula Ti (OR) aX 4-aThe magnesium solution of preparation in the liquid mixture treatment step (2) of the titanium compound of (wherein R is the alkyl with 1-10 carbon atom, and X is a halogen atom, and a is the integer between 0 to 4) expression, but recrystallization granules of catalyst.
Example at the titanium compound of above-mentioned general formula is titanium tetrahalide such as TiCl 4, TiBr 4And TiI 4Three halogenated alkoxy titaniums such as Ti (OCH 3) Cl 3, Ti (OC 2H 5) Cl 3, Ti (OC 2H 5) Br 3And Ti (O (i-C 4H 9)) Br 3Dihalide titan-alkoxide such as Ti (OCH 3) 2Cl 2, Ti (OC 2H 5) 2Cl 2, Ti (O (i-C 4H 9)) 2Cl 2And Ti (OC 2H 5) 2Br 2With four titan-alkoxides such as Ti (OCH 3) 4, Ti (OC 2H 5) 4And Ti (OC 4H 9) 4Also can use the mixture of above-mentioned titanium compound.Preferred titanium compound is the titanium compound that contains halogen, or more preferably titanium tetrachloride.
Compound halo alkane is to have the hydrocarbon compound of 1-20 carbon atom and can use this compound separately or with the form of mixtures of two or more above-claimed cpds.
The example of halogenated alkane is: monochloro methane, methylene dichloride, trichloromethane, tetrachloromethane, monochlorethane, 1,2-ethylene dichloride, a chloropropane, a chlorobutane, the secondary butane of a chlorine, a chlorolifarina, a chlorine hexanaphthene, chlorobenzene, a monobromethane, a N-PROPYLE BROMIDE, a n-butyl bromide or a methyl iodide.Preferred compound halo alkane is the chloroparaffin compound.
The suitable amounts of the titanium compound that uses in the recrystallization of magnesium solution and the mixture of compound halo alkane is about 0.1-200mol, or preferred 0.1-100mol, or more preferably 0.2-80mol/mol magnesium compound.Titanium compound is about 1 with the mol ratio of mixing of compound halo alkane: 0.05-0.95, or more preferably 1: 0.1-0.8.
When the mixture reaction of magnesium compound solution and titanium compound and compound halo alkane, the form of the solid ingredient of gained recrystallization and size depend on reaction conditions widely.
Therefore, in order to control particle shape, can preferably under enough low temperature,, produce solid substance composition by making the mixture reaction of magnesium compound solution and titanium compound and compound halo alkane.Temperature of reaction can be pact-70-70 ℃, or more preferably from about-and 50-50 ℃.After exposure-response, the temperature of reaction that slowly raises so that under 50-150 ℃, is reacted fully through about 0.5-5 hour time length.
The solid catalyst particle that obtains by above-mentioned explanation can be further and extra titanium compound reaction.Employed titanium compound can be the halogenated alkoxy titanium of halogenated titanium or the alkoxy-functional that has 1-20 carbon atom.Also can optionally use the mixture of these compounds.In the middle of these compounds, halogenated titanium or or the halogenated alkoxy titanium compound that has an alkoxy-functional of 1-8 carbon be suitable and more preferably titanium tetrachloride.
Can be used for the polymerization and the copolymerization of ethene according to the catalyzer of method preparation preparation described herein.Especially, in the homopolymerization of ethene, and in ethene and copolymerization, can advantageously use this catalyzer with the alpha-olefin of three or more carbon atoms such as propylene, 1-butylene, 1-amylene, 4-methyl-1-pentene or 1-hexene.
Contain following catalyst system by use, can use the polyreaction of catalyzer described herein, this catalyst system comprises: the solid titanium composition catalyst described herein that (I) comprises magnesium, titanium, halogen and electron donor(ED); (II) comprise the organometallic compound of the metal of II in the periodictable or III family.
Available formula M R nExpression organometallic compound (II), wherein M is the metal component of II or IIIA family in the periodictable, and as magnesium, calcium, zinc, boron, aluminium or gallium, R is the alkyl with 1-20 carbon atom, as methyl, ethyl, butyl, hexyl, octyl group or decyl and n is the valence of above-mentioned metal component.In some embodiments, organometallic compound is the trialkylaluminium with alkyl of 1-6 carbon atom, as triethyl aluminum and triisobutyl aluminium or its mixture.Optionally, also can use organo-aluminium compound, as ethylaluminium dichloride, diethylaluminum chloride, ethyl aluminium sesqui chloride or diisobutylaluminium hydride with one or more halogen or hydridization group.
Before solid titanium composition catalyst component described herein is used in polyreaction, can with ethene or alpha-olefin pre-polymerization.Can under varsol such as hexane, under enough low temperature, carry out pre-polymerization under the pressure of ethene or alpha-olefin and in the presence of described catalyst component and organo-aluminium compound such as triethyl aluminum.Help to improve polymer form after the polymerization by keep pre-polymerization that catalyst form carries out with the surrounded granules of catalyst.After pre-polymerization, the weight ratio of polymkeric substance and catalyzer is common about 0.1: 1-20: 1.
Can be not existing under the organic solvent, by vapour phase polymerization or mass polymerization, or carry out polyreaction by the liquid phase slurry polymerization existing under the organic solvent.Yet, can carry out these polymerization processs not existing oxygen, water maybe may play under other compound of paralyser effect.
In some embodiments, in the liquid phase slurry polymerization, the concentration of the solid titanium composition catalyst in polymerization reaction system is the titanium atom of about 0.001-5mmol in the 1L solvent, or the titanium atom of 0.001-0.5mmol more preferably from about.As solvent, can use following compound or its mixture: alkane such as pentane, hexane, heptane, octane, octane-iso, hexanaphthene and methylcyclohexane; Alkylaromatics such as toluene, dimethylbenzene, ethylbenzene, isopropyl benzene, ethyltoluene, n-propylbenzene and diethylbenzene; With halogenated aromatic substance such as chlorobenzene, chloronaphthalene and orthodichlorobenzene.
Under the situation of vapour phase polymerization, the amount of solid titanium composition catalyst (I) is the titanium atom of about 0.001-5mmol, the preferred titanium atom of about 0.001-1.0mmol, or the titanium atom of 0.01-0.5mmol/L polymerization reactant more preferably from about.The preferred concentration of organometallic compound (II) is the aluminium atom of about 1-2000mol, or the titanium atom in the aluminium atom of 5-500mol/mol catalyzer (I) more preferably from about.
In order to ensure high polymerization rate, can under sufficiently high temperature, carry out polyreaction, and no matter polymerization technique.Usually, suitable temperature is about 20-200 ℃, or more preferably from about 20-95 ℃.Monomeric convenient pressure is 1-100atm in polymerization process, or more preferably 2-50atm.
Embodiment
Comprise following embodiment, with some embodiments of demonstrating.Those skilled in the art should be appreciated that in following examples disclosed technology represents the technology of being found, go on well in its disclosed herein practice.Yet those skilled in the art should be appreciated that according to content disclosed in this invention, can make many variations in disclosed specific embodiments, and still obtain same or similar result, and not break away from the spirit and scope of the present invention.
Embodiment 1
The preparation of solid titanium composition catalyst
Prepare solid titanium composition catalyst component in the following manner:
(i) preparation of magnesium solution
In the 1.0L reactor of being furnished with mechanical stirrer and purging, introduce 19.0g magnesium chloride and 400ml decane, after under 700rpm, stirring, add the 120ml 2-Ethylhexyl Alcohol and under 120 ℃ temperature, reacted 3 hours with nitrogen atmosphere.Will be by the homogeneous phase solution cool to room temperature (25 ℃) of reaction acquisition.
(ii) magnesium solution and the ester of hydroxyl and contacting of alkoxy-silicon compound
In being cooled to 25 ℃ (i), add 1.2ml methacrylic acid 2-hydroxyl ethyl ester and 12.0ml tetrem silicon oxide in the magnesium compound solution of preparation and reaction was carried out 1 hour.
(iii) and (iv): handle and handle with titanium compound with the mixture of titanium compound and compound halo alkane
Adjust to after 15 ℃ at the solution temperature that will (ii) prepare by step, through 1 hour to the mixture solution that wherein splashes into 40ml titanium tetrachloride and 40ml tetrachloromethane.Finish drip technology after, the temperature of reactor was elevated to 70 ℃ and kept 1 hour under this temperature through 1 hour.After stirring, remove the supernatant liquid of solution and on residual solid, add 300ml decane and 100ml titanium tetrachloride according to the order of sequence.Then, temperature is elevated to 90 ℃, and kept 2 hours.In reactor cooling after room temperature and use the 400ml hexane wash, up to the free titanium tetrachloride of removing remained unreacted fully.Titanium content in the prepared solid catalyst is 3.8%.
Polymerization
In baking oven, after the drying, assemble the 2l high-pressure reactor while hot.By alternately three times with the nitrogen purging reactor with reactor is vacuumized, make reactor be adjusted into nitrogen atmosphere, introduce the 1000ml normal hexane then and after the solid titanium composition catalyst of introducing 1mmol triethyl aluminum and 0.03mmol titanium atom, add 1000ml hydrogen.Using agitator, when stirring temperature of reactor is being elevated to 80 ℃ and the pressure of adjusting ethene and is 80psi and carried out polymerization 1 hour with 700rpm.After polymerization, the temperature of reactor is reduced to room temperature and in the polymeric material, adds excess ethyl alcohol solution.Separate and collect the polymkeric substance produced and under 50 ℃ in vacuum drying oven drying at least 6 hours, obtain the polyethylene of white powder form.
Estimate
Calculate the polymerization activity of catalyzer with the polymkeric substance of being produced (kg) with the weight ratio of employed catalytic amount (g), and measure the tap density (g/ml) of the polymkeric substance of being produced and the results are shown in Table 1.
In addition, in order to estimate hydrogen reaction (it is the intensity of variation of the molecular weight of the polymkeric substance produced with employed amounts of hydrogen), measure melt index (g/10min) and the results are shown in Table 1 according to the method described in the ASTM D 1238.Usually, when molecular weight diminished, it is big that melt index becomes.
Embodiment 2
Prepare catalyzer in the mode identical with embodiment 1, different is by the mixture solution that uses 40ml titanium tetrachloride and 40ml trichloromethane carry out step (iii) in the processing of mixture of titanium compound and compound halo alkane.The titanium content of prepared catalyzer is 3.9%.In the mode identical, by using this catalyzer to carry out polymerization and the results are shown in Table 1 with embodiment 1.
Embodiment 3
Prepare catalyzer in the mode identical with embodiment 1, different is by the mixture solution that uses 40ml titanium tetrachloride and 40ml tertiary butyl chloride carry out step (iii) in the processing of mixture of titanium compound and compound halo alkane.The titanium content of prepared catalyzer is 3.5%.In the mode identical, by using this catalyzer to carry out polymerization and the results are shown in Table 1 with embodiment 1.
Embodiment 4
Prepare catalyzer in the mode identical with embodiment 1, different is by using 40ml titanium tetrachloride and 40ml 1, the mixture solution of 2-ethylene dichloride carry out step (iii) in the processing of mixture of titanium compound and compound halo alkane.The titanium content of prepared catalyzer is 4.1%.In the mode identical, by using this catalyzer to carry out polymerization and the results are shown in Table 1 with embodiment 1.
Embodiment 5
Prepare catalyzer in the mode identical with embodiment 1, different is by the mixture solution that uses 40ml titanium tetrachloride and 40ml chlorobenzene carry out step (iii) in the processing of mixture of titanium compound and compound halo alkane.The titanium content of prepared catalyzer is 4.2%.In the mode identical, by using this catalyzer to carry out polymerization and the results are shown in Table 1 with embodiment 1.
Embodiment 6
Prepare catalyzer in the mode identical with embodiment 1, different is by the mixture solution that uses 60ml titanium tetrachloride and 60ml tetrachloromethane carry out step (iii) in the processing of mixture of titanium compound and compound halo alkane.The titanium content of prepared catalyzer is 4.1%.In the mode identical, by using this catalyzer to carry out polymerization and the results are shown in Table 1 with embodiment 1.
Embodiment 7
Prepare catalyzer in the mode identical with embodiment 1, different is by the mixture solution that uses 80ml titanium tetrachloride and 80ml tetrachloromethane carry out step (iii) in the processing of mixture of titanium compound and compound halo alkane.The titanium content of prepared catalyzer is 4.5%.In the mode identical, by using this catalyzer to carry out polymerization and the results are shown in Table 1 with embodiment 1.
Embodiment 8
Prepare catalyzer in the mode identical with embodiment 1, different is by the mixture solution that uses 60ml titanium tetrachloride and 30ml tetrachloromethane carry out step (iii) in the processing of mixture of titanium compound and compound halo alkane.The titanium content of prepared catalyzer is 4.5%.In the mode identical, by using this catalyzer to carry out polymerization and the results are shown in Table 1 with embodiment 1.
Embodiment 9
Prepare catalyzer in the mode identical with embodiment 1, different is by the mixture solution that uses 40ml titanium tetrachloride and 80ml tetrachloromethane carry out step (iii) in the processing of mixture of titanium compound and compound halo alkane.The titanium content of prepared catalyzer is 3.7%.In the mode identical, by using this catalyzer to carry out polymerization and the results are shown in Table 1 with embodiment 1.
Embodiment 10
Prepare catalyzer in the mode identical with embodiment 1, different is by the mixture solution that uses 60ml titanium tetrachloride and 30ml trichloromethane carry out step (iii) in the processing of mixture of titanium compound and compound halo alkane.The titanium content of prepared catalyzer is 4.4%.In the mode identical, by using this catalyzer to carry out polymerization and the results are shown in Table 1 with embodiment 1.
Embodiment 11
Prepare catalyzer in the mode identical with embodiment 1, different is by the mixture solution that uses 40ml titanium tetrachloride and 80ml trichloromethane carry out step (iii) in the processing of mixture of titanium compound and compound halo alkane.The titanium content of prepared catalyzer is 3.5%.In the mode identical, by using this catalyzer to carry out polymerization and the results are shown in Table 1 with embodiment 1.
Embodiment 12
Prepare catalyzer in the mode identical with embodiment 1, different is by the mixture solution that uses 60ml titanium tetrachloride and 30ml chlorobenzene carry out step (iii) in the processing of mixture of titanium compound and compound halo alkane.The titanium content of prepared catalyzer is 4.6%.In the mode identical, by using this catalyzer to carry out polymerization and the results are shown in Table 1 with embodiment 1.
Embodiment 13
Prepare catalyzer in the mode identical with embodiment 1, different is by the mixture solution that uses 40ml titanium tetrachloride and 80ml chlorobenzene carry out step (iii) in the processing of mixture of titanium compound and compound halo alkane.The titanium content of prepared catalyzer is 4.1%.In the mode identical, by using this catalyzer to carry out polymerization and the results are shown in Table 1 with embodiment 1.
Embodiment 14
Prepare catalyzer in the mode identical with embodiment 1, different is the following processing of carrying out the mixture of (iii) middle titanium compound of step and compound halo alkane: with dripping the mixture of 40ml titanium tetrachloride and 40ml tetrachloromethane in 1 hour, make this solution left standstill 1 hour then; Then add the 100ml titanium tetrachloride and be warmed up to after 90 ℃, solution was kept under this temperature 2 hours.The titanium content of prepared catalyzer is 3.9%.In the mode identical, by using this catalyzer to carry out polymerization and the results are shown in Table 1 with embodiment 1.
Comparative Examples 1
Prepare catalyzer in the mode identical with embodiment 1, different is step (ii) in, use 10.0ml tetrem silicon oxide, but do not use methacrylic acid 2-hydroxyl ethyl ester.The titanium content of prepared catalyzer is 4.1%.In the mode identical, by using this catalyzer to carry out polymerization and the results are shown in Table 1 with embodiment 1.
Comparative Examples 2
Prepare catalyzer in the mode identical with embodiment 1, different is step (ii) in, use 1.2ml methacrylic acid 2-hydroxyl ethyl ester, but do not use the tetrem silicon oxide.The titanium content of prepared catalyzer is 3.7%.In the mode identical, by using this catalyzer to carry out polymerization and the results are shown in Table 1 with embodiment 1.
Comparative Examples 3
Prepare catalyzer in the mode identical with embodiment 1, different is step (ii) in, do not use methacrylic acid 2-hydroxyl ethyl ester and tetrem silicon oxide.The titanium content of prepared catalyzer is 4.5%.In the mode identical, by using this catalyzer to carry out polymerization and the results are shown in Table 1 with embodiment 1.
Comparative Examples 4
Prepare catalyzer in the mode identical with embodiment 1, different is step (iii) in, use the 40ml titanium tetrachloride, rather than the mixture of titanium tetrachloride and tetrachloromethane.The titanium content of prepared catalyzer is 4.6%.In the mode identical, by using this catalyzer to carry out polymerization and the results are shown in Table 1 with embodiment 1.
Comparative Examples 5
Prepare catalyzer in the mode identical with embodiment 1, different is step (iii) in, use the 40ml silicon tetrachloride, rather than the mixture of titanium tetrachloride and tetrachloromethane.The titanium content of prepared catalyzer is 3.4%.In the mode identical, by using this catalyzer to carry out polymerization and the results are shown in Table 1 with embodiment 1.
Comparative Examples 6
Prepare catalyzer in the mode identical with embodiment 1, different is step (iii) in, use the 30ml triethyl aluminum, rather than the mixture of titanium tetrachloride and tetrachloromethane.The titanium content of prepared catalyzer is 4.4%.In the mode identical, by using this catalyzer to carry out polymerization and the results are shown in Table 1 with embodiment 1.
Table 1
Active (kg PE/g catalyzer) Tap density (g/ml) MI(g/10min)
E1 4.2 0.41 2.6
E2 4.3 0.39 2.5
E3 3.8 0.40 2.5
E4 3.7 0.38 2.2
E5 4.4 0.39 2.4
E6 4.3 0.37 2.7
E7 4.1 0.35 2.2
E8 4.4 0.37 2.8
E9 4.2 0.41 2.9
E10 4.4 0.37 2.4
E11 4.1 0.38 2.5
E12 4.5 0.37 2.6
E13 4.3 0.39 2.4
E14 4.4 0.34 2.7
CE1 3.2 0.30 1.6
CE2 3.4 0.31 1.5
CE3 3.3 0.24 0.8
CE4 3.1 0.29 1.6
CE5 3.2 0.24 1.5
CE6 3.5 0.23 1.1
*E: embodiment, CE: Comparative Examples
Can find out that from table 1 vinyl polymerization described herein and copolymerization demonstrate catalytic activity than Comparative Examples high 30% with catalyzer.In addition, the polymkeric substance by Catalyst Production described herein has high tap density, and has high melt index, thereby shows the hydrogen reaction height of catalyzer.
Industrial applicibility
Described in specification, by use this catalyst in the polymerization of ethene and in the copolymerization of ethene and other alpha-olefin, owing to the high activity of catalyst, but therefore high productivity is produced polymer, and can not need remove catalyst residue. Can demonstrate good physical property such as high-bulk-density and flowability by the polymer that uses this Catalyst Production, and the high hydrogen reaction of catalyst is so that more easily operate this technique. In a word, solid titanium composition catalyst described herein is very useful as polymerization and the copolymerization catalyst of ethene.
Consider this specification sheets, the further modification of each side of the present invention and alternate embodiment are obvious to those skilled in the art.Therefore, think that this specification sheets only is to exemplify and in order to instruct those technician of the present invention to implement general fashion of the present invention.Be to be understood that form of the present invention shown here and described regards present preferred embodiment as.Alternative this place of various elements and material exemplify with described those, can put upside down each several part and technology, with can utilize features more of the present invention independently, all these are obvious after benefiting from this specification sheets of the present invention to one skilled in the art.Can make many variations to element described herein, and not break away from the spirit and scope of following claims of the present invention.

Claims (12)

1. the vinyl polymerization and the copolymerization catalyzer of the method preparation by containing following step:
(1) by making halogenated magnesium compound and alcohol reaction, preparation magnesium solution;
(2) make this magnesium solution and ester cpds with at least one hydroxyl and silicon compound reaction, produce the solution that contains magnesium component with at least one alkoxyl group; With
(3) by making the solution that contains magnesium component and the mixture reaction of titanium compound and compound halo alkane, produce solid titanium catalyst, wherein titanium compound is with general formula Ti (OR) aX 4-aExpression, wherein R is the alkyl with 1-10 carbon atom, and X is a halogen atom, and a is the integer between 0 to 4.
2. the catalyzer of claim 1, wherein this method further comprises and makes solid titanium catalyst and extra titanium compound reaction.
3. the catalyzer of claim 1, the ester cpds that wherein has at least one hydroxyl be the unsaturated aliphatic acid esters with at least one hydroxyl, the aliphatic mono with at least one hydroxyl or polyester, have the aromatic ester of at least one hydroxyl or have the alicyclic ester of at least one hydroxyl.
4. the catalyzer of claim 1, the silicon compound that wherein has an alkoxyl group is a general formula R 1 aR 2 bR 3 cR 4 dSi (OR 5) eThe compound of expression, wherein R 1, R 2, R 3, R 4, and R 5Independently of one another for having the alkyl of 1-12 carbon atom and a wherein, b, c, d and e are 0 to 4 integer and a wherein, b, and c, d and e satisfy equation a+b+c+d+e=4.
5. the catalyzer of claim 1, wherein compound halo alkane is the hydrocarbon compound that contains at least one halogen and have 1-20 carbon atom.
6. the catalyzer of claim 1, wherein the consumption of the mixture of titanium compound and compound halo alkane be the 0.1-200mol/mol halogenated magnesium compound and wherein the mol ratio of mixing of compound halo alkane and titanium compound be 0.05-0.95.
7. one kind prepares the polymerization of ethene and the method that catalyzer is used in copolymerization, and it comprises:
(1) by making halogenated magnesium compound and alcohol reaction, preparation magnesium solution;
(2) make this magnesium solution and ester cpds with at least one hydroxyl and silicon compound reaction, produce the solution that contains magnesium component with at least one alkoxyl group; With
(3) by making the solution that contains magnesium component and the mixture reaction of titanium compound and compound halo alkane, produce solid titanium catalyst, wherein titanium compound is with general formula Ti (OR) aX 4-aThe expression and wherein R be alkyl with 1-10 carbon atom, X is a halogen atom, a is the integer between 0 to 4.
8. the method for claim 7, wherein this method further comprises and makes solid titanium catalyst and extra titanium compound reaction.
9. the method for claim 7, the ester cpds that wherein has at least one hydroxyl is the unsaturated aliphatic acid esters with at least one hydroxyl; Aliphatic mono or polyester with at least one hydroxyl; Aromatic ester with at least one hydroxyl; Or has an alicyclic ester of at least one hydroxyl.
10. the method for claim 7, the silicon compound that wherein has an alkoxyl group is a general formula R 1 aR 2 bR 3 cR 4 dSi (OR 5) eThe compound of expression, wherein R 1, R 2, R 3, R 4, and R 5Independently of one another for having the alkyl of 1-12 carbon atom and a wherein, b, c, d and e are 0 to 4 integer and a wherein, b, and c, d and e satisfy equation a+b+c+d+e=4.
11. the method for claim 7, wherein compound halo alkane is the hydrocarbon compound that contains at least one halogen and have 1-20 carbon atom.
12. the method for claim 7, wherein the consumption of the mixture of titanium compound and compound halo alkane be the 0.1-200mol/mol halogenated magnesium compound and wherein the mol ratio of mixing of compound halo alkane and titanium compound be 0.05-0.95.
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